Resin composition for modeling material, light curing molding ink set, and method for manufacturing optically shaped article

ABSTRACT

There is provided a resin composition for a modeling material, used for shaping a modeling material by a manufacturing method for light curing molding using an ink-jet scheme, comprising (A) an ethylenic unsaturated monomer as a photocuring component, (B) a photopolymerization initiator, and (C) a surface adjusting agent, wherein the resin composition for a modeling material has surface tension Mt of 26.0 to 33.0 mN/m, and the resin composition for a modeling material has surface tension Mst represented by the following (i) expression of 33.0 mN/m or more, and this resin composition for a modeling material 4a can afford a light cured article having the good dimensional accuracy.

TECHNICAL FIELD

The present invention relates to a resin composition for a modelingmaterial, a light curing molding ink set comprising the resincomposition for a modeling material, and a method for manufacturing alight cured article using the light curing molding ink set.

BACKGROUND ART

Conventionally, as a method for making a stereoscopically shapedproduct, a shaping method using a photocurable resin composition whichcures by irradiating ultraviolet rays or the like has widely been known.Specifically, in such a shaping method, a cured layer having apredetermined shape is formed by irradiating the photocurable resincomposition with ultraviolet rays or the like to cure it. Thereafter, anew cured layer is formed by further feeding the photocurable resincomposition on the cured layer to cure it. By repeatedly performing thestep as described above, a stereoscopically shaped product is made.

Among the shaping methods as described above, in recent years, there hasbeen reported an optical shaping method by an ink-jet system bydischarging the photocurable resin composition from a nozzle,irradiating ultraviolet rays or the like immediately after the dischargeto cure it, thereby, forming a cured layer having a predetermined shape(hereinafter referred to as manufacturing method for light curingmolding using an ink-jet scheme) (JP-A-2004-255839, JP-A-2010-155889,JP-A-2010-155926 and JP-A-2012-111226). The manufacturing method forlight curing molding using an ink-jet scheme does not need installationof a large-scale resin liquid tank for storing the photocurable resincomposition and a darkroom. For that reason, a shaping apparatus can beminiaturized as compared with the conventional method. The manufacturingmethod for light curing molding using an ink-jet scheme has been paidattention as a shaping method which is realized by a 3D printer that canfreely make a stereoscopically shaped product, based on CAD (ComputerAided Design) data.

In the manufacturing method for light curing molding using an ink-jetscheme, when a light cured article having a complicated shape such as ahollow shape is shaped, in order to support a modeling material, themodeling material and a supporting material are formed in combination(JP-A-2004-255839, JP-A-2010-155889 and JP-A-2012-111226). Thesupporting material is made by irradiating the photocurable resincomposition with ultraviolet rays or the like to cure it, like themodeling material. After the modeling material has been made, thesupporting material can be removed by physically peeling the supportingmaterial, or dissolving the supporting material in an organic solvent orwater.

In the manufacturing method for light curing molding using an ink-jetscheme using the modeling material and the supporting material, thecured layer is formed, for example, by the following method. First, bydischarging a resin composition for a modeling material and a resincomposition for a supporting material from an ink-jet head, a resincomposition layer in which a layer composed of the resin composition fora modeling material and the resin composition for a supporting materialare contiguous is formed. And, in order to smooth an upper surface ofthe resin composition layer, a roller is used to remove the extra resincomposition for a modeling material and resin composition for asupporting material. Finally, by irradiating these resin compositionswith light using a light source, the resin compositions are cured.Thereby, a cured layer composed of the modeling material and thesupporting material is formed.

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

However, the conventional light cured article which is obtained by usingthe resin composition for a modeling material and the resin compositionfor a supporting material had a problem that the dimensional accuracy isreduced.

The present invention was made in view of the above-mentioned presentsituation, and an object thereof is to provide a resin composition for amodeling material by which a light cured article having the gooddimensional accuracy can be obtained, a light curing molding ink setcomprising the resin composition for a modeling material, and a methodfor manufacturing a light cured article using the light curing moldingink set.

Solutions to the Problems

The present inventors intensively studied the cause for reduction in thedimensional accuracy of the light cured article. As a result, thepresent inventors obtained the finding that in the light cured articlehaving the reduced dimensional accuracy, by movement of one of the resincomposition for a modeling material and the resin composition for asupporting material to the other side at an interface between the layercomposed of the resin composition for a modeling material and the layercomposed of the resin composition for a supporting material, blur(bleeding) is generated at the interface. That is, the present inventorsobtained the finding that bleeding which is generated at the interfacebetween the layer composed of the resin composition for a modelingmaterial and the layer composed of the resin composition for asupporting material is one of the causes for reduction in thedimensional accuracy of the light cured article.

The present invention was made based on the above-mentioned finding, andthe gist thereof is as follows:

[1] A resin composition for a modeling material, used for shaping amodeling material by a manufacturing method for light curing moldingusing an inkjet scheme, comprising (A) an ethylenic unsaturated monomeras a photocuring component, (B) a photopolymerization initiator, and (C)a surface adjusting agent, wherein the resin composition for a modelingmaterial has surface tension Mt of 26.0 to 33.0 mN/m, and the resincomposition for a modeling material has surface tension Mst representedby the following (i) expression of 33.0 mN/m or more.

[Mathematic  1]                                     $\begin{matrix}{{Mst} = \frac{\begin{matrix}{\Sigma \mspace{14mu}\left( {{Surface}\mspace{14mu} {tension}\mspace{14mu} {of}\mspace{14mu} {each}\mspace{14mu} {photocuring}\mspace{14mu} {component} \times} \right.} \\\left. {{content}\mspace{14mu} {of}\mspace{14mu} {each}\mspace{14mu} {photocuring}\mspace{14mu} {component}} \right)\end{matrix}}{{Total}\mspace{14mu} {content}\mspace{14mu} {of}\mspace{14mu} {photocuring}\mspace{14mu} {components}}} & (i)\end{matrix}$

Effects of the Invention

According to the present invention, there can be provided a resincomposition for a modeling material by which a light cured articlehaving the good dimensional accuracy can be obtained by suppressinggeneration of bleeding at an interface between a layer composed of aresin composition for a modeling material and a layer composed of aresin composition for a supporting material, a light curing molding inkset comprising the resin composition for a modeling material, and amethod for manufacturing a light cured article using the light curingmolding ink set.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a view schematically showing a step (I) in the method formanufacturing a light cured article of the present embodiment.

FIG. 2 is a view schematically showing a step (II) in the method formanufacturing a light cured article of the present embodiment.

FIG. 3 is a view schematically showing a cured product 6 composed of amodeling material 4 and a supporting material 5, which was obtained byrepeatedly performing steps (I) and (II) in the method for manufacturinga light cured article of the present embodiment.

FIG. 4 is a view schematically showing a step (III) in the method formanufacturing a light cured article of the present embodiment.

FIG. 5 (a) is a top view of a cured product which is obtained using eachresin composition for a modeling material and each resin composition fora supporting material shown in Table 1. FIG. 5 (b) is a line A-Across-sectional view of FIG. 5 (a).

EMBODIMENTS OF THE INVENTION

One embodiment of the present invention (hereinafter, also referred toas present embodiment) will be illustrated in detail below. The presentinvention is not limited to the following contents. In addition, in thefollowing illustration, “(meth)acrylate” is a generic name of acrylateand methacrylate, and means one or both of acrylate and methacrylate.This also applies to “(meth)acryloyl” and “(meth)acryl”.

[1] The resin composition for a modeling material of the presentembodiment is a resin composition for a modeling material, used forshaping a modeling material by a manufacturing method for light curingmolding using an ink-jet scheme, comprising (A) an ethylenic unsaturatedmonomer as a photocuring component, (B) a photopolymerization initiator,and (C) a surface adjusting agent, wherein the resin composition for amodeling material has surface tension Mt of 26.0 to 33.0 mN/m, and theresin composition for a modeling material has surface tension Mstrepresented by the following (i) expression of 33.0 mN/m or more.

[Mathematic  2]                                     $\begin{matrix}{{Mst} = \frac{\begin{matrix}{\Sigma \mspace{14mu}\left( {{Surface}\mspace{14mu} {tension}\mspace{14mu} {of}\mspace{14mu} {each}\mspace{14mu} {photocuring}\mspace{14mu} {component} \times} \right.} \\\left. {{content}\mspace{14mu} {of}\mspace{14mu} {each}\mspace{14mu} {photocuring}\mspace{14mu} {component}} \right)\end{matrix}}{{Total}\mspace{14mu} {content}\mspace{14mu} {of}\mspace{14mu} {photocuring}\mspace{14mu} {components}}} & (i)\end{matrix}$

[2] In the resin composition for a modeling material according to [1],the (A) component comprises 70 parts by weight or less of amonofunctional ethylenic unsaturated monomer, based on 100 parts byweight of the whole resin composition for a modeling material.

[3] In the resin composition for a modeling material according to [2],the content of the monofunctional ethylenic unsaturated monomer is 5 to70 parts by weight, based on 100 parts by weight of the whole resincomposition for a modeling material.

[4] In the resin composition for a modeling material according to anyone of [1] to [3], the (A) component comprises 70 parts by weight orless of a polyfunctional ethylenic unsaturated monomer, based on 100parts by weight of the whole resin composition for a modeling material.

[5] In the resin composition for a modeling material according to [4],the content of the polyfunctional ethylenic unsaturated monomer is 20 to70 parts by weight, based on 100 parts by weight of the whole resincomposition for a modeling material.

[6] In the resin composition for a modeling material according to anyone of [1] to [5], the content of the (A) component is 80 to 99 parts byweight, based on 100 parts by weight of the whole resin composition fora modeling material.

[7] In the resin composition for a modeling material according to anyone of [1] to [6], the resin composition for a modeling material furthercontains an oligomer as (D) a photocuring component.

[8] In the resin composition for a modeling material according to [7],the content of the (D) component is 10 to 45 parts by weight, based on100 parts by weight of the whole resin composition for a modelingmaterial.

[9] In the resin composition for a modeling material according to anyone of [1] to [8], the resin composition for a modeling material has thesurface tension Mst of 33.0 to 40.0 mN/m.

[10] The light curing molding ink set of the present embodiment is alight curing molding ink set used for a manufacturing method for lightcuring molding using an ink-jet scheme, comprising a combination of theresin composition for a modeling material as defined in any one of [1]to [9], and a resin composition for a supporting material used forshaping the supporting material, wherein the resin composition for asupporting material contains (E) a water-soluble monofunctionalethylenic unsaturated monomer, (F) polyalkylene glycol comprising anoxyethylene group and/or an oxypropylene group, (B) aphotopolymerization initiator, and (C) a surface adjusting agent.

[11] In the light curing molding ink set according to [10], the contentof the (E) component is 20 to 50 parts by weight, based on 100 parts byweight of the whole resin composition for a supporting material.

[12] In the light curing molding ink set according to [10] or [11], thecontent of the (F) component is 20 to 49 parts by weight, based on 100parts by weight of the whole resin composition for a supportingmaterial.

[13] In the light curing molding ink set according to any one of [10] to[12], a number average molecular weight Mn of the (F) component is 100to 5,000.

[14] In the light curing molding ink set according to any one of [10] to[13], surface tension St of the resin composition for a supportingmaterial is 24.0 to 33.0 mN/m.

[15] The method for manufacturing a light cured article of the presentembodiment is a method for manufacturing a light cured article using thelight curing molding ink set as defined in any one of [10] to [14] by amanufacturing method for light curing molding using an ink-jet scheme,comprising a step (I) of discharging a resin composition for a modelingmaterial and a resin composition for a supporting material from anink-jet head, so that a resin composition layer in which a layercomposed of the resin composition for a modeling material and a layercomposed of the resin composition for a supporting material are arrangedcontiguously, a step (II) of photocuring the resin composition for amodeling material and the resin composition for a supporting materialconstituting the resin composition layer, respectively, thereby,obtaining a modeling material and a supporting material, and a step(III) of removing the supporting material, thereby, obtaining a lightcured article.

1. Resin Composition for Modeling Material

The resin composition for a modeling material contains (A) an ethylenicunsaturated monomer as a photocuring component, (B) aphotopolymerization initiator, and (C) a surface adjusting agent.

<(A) Ethylenic Unsaturated Monomer>

The (A) ethylenic unsaturated monomer is a photocuring component havingproperty that it cures by energy rays. The (A) component comprises atleast one of a monofunctional ethylenic unsaturated monomer having oneethylenic double bond in a molecule, and a polyfunctional ethylenicunsaturated monomer having two or more ethylenic double bonds in amolecule. Additionally, the monofunctional ethylenic unsaturated monomercomprises at least one of a water-insoluble monofunctional ethylenicunsaturated monomer, and a water-soluble monofunctional ethylenicunsaturated monomer.

Examples of the water-insoluble monofunctional ethylenic unsaturatedmonomer include, for example, linear or branched alkyl (meth)acrylateshaving 4 to 30 carbon atoms [e.g. methyl (meth)acrylate, ethyl(meth)acrylate, isobutyl (meth)acrylate, lauryl (meth)acrylate, stearyl(meth)acrylate, isostearyl (meth)acrylate, t-butyl (meth)acrylate etc.],alicycle-containing (meth)acrylates having 6 to 20 carbon atoms [e.g.cyclohexyl (meth)acrylate, 4-t-cyclohexyl (meth)acrylate, isobornyl(meth)acrylate, 4-t-butylcyclohexanol (meth)acrylate,3,3,5-trimethylcyclohexanol (meth)acrylate, phenoxyethyl (meth)acrylateetc.], heterocycle-containing (meth)acrylates having 5 to 20 carbonatoms [e.g. tetrahydrofurfuryl (meth)acrylate,4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane,4-(meth)acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, adamantyl(meth)acrylate, cyclic trimethylolpropaneformal (meth)acrylate etc.] andthe like. These may be used alone, or two or more may be usedconcurrently. Among them, from a view point that curability of the resincomposition for a modeling material is improved, the water-insolublemonofunctional ethylenic unsaturated monomer is preferably4-t-butylcyclohexanol (meth)acrylate, 3,3,5-trimethylcyclohexanol(meth)acrylate, or phenoxyethyl (meth)acrylate.

Examples of the water-soluble monofunctional ethylenic unsaturatedmonomer include, for example, hydoxy group-containing (meth)acrylateshaving 5 to 15 carbon atoms [e.g. hydroxyethyl (meth)acrylate,hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate etc.],hydroxy group-containing (meth)acrylates having Mn of 200 to 1,000[polyethylene glycol mono(meth)acrylate, monoalkoxy (having 1 to 4carbon atoms) polyethylene glycol mono(meth)acrylate, polypropyleneglycol mono(meth)acrylate, monoalkoxy (having 1 to 4 carbon atoms)polypropylene glycol mono(meth)acrylate, mono(meth)acrylate of PEG-PPGblock polymer etc.], (meth)acrylamide derivatives having 3 to 15 carbonatoms [(meth)acrylamide, N-methyl(meth)acrylamide,N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide,N-butyl(meth)acrylamide, N, N′-dimethyl(meth)acrylamide, N,N′-diethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide,N-hydroxypropyl(meth)acrylamide, N-hydroxybutyl(meth)acrylamide etc.],(meth)acryloylmorpholine and the like. These may be used alone, or twoor more may be used concurrently. Among them, from a view point ofimprovement in curability of the resin composition for a supportingmaterial and a view point of skin low irritation to a human body, thewater-soluble monofunctional ethylenic unsaturated monomer is preferably(meth)acryloylmorpholine.

From a view point that an ink is maintained at the low viscosity, thetotal content of the water-insoluble monofunctional ethylenicunsaturated monomer and the water-soluble monofunctional ethylenicunsaturated monomer (i.e. the content of the monofunctional ethylenicunsaturated monomer) is preferably 5 parts by weight or more, morepreferably 30 parts by weight or more, and particularly preferably 50parts by weight or more, based on 100 parts by weight of the whole resincomposition for a modeling material. Additionally, the content of themonofunctional ethylenic unsaturated monomer is preferably 70 parts byweight or less, and more preferably 69 parts by weight or less, based on100 parts by weight of the whole resin composition for a modelingmaterial. In addition, when two or more of the monofunctional ethylenicunsaturated monomers are contained, the content is a total of thecontents of respective monofunctional ethylenic unsaturated monomers.

Examples of the polyfunctional ethylenic unsaturated monomer include,for example, Tinier or branched alkylene glycol di(meth)acrylates oralkylene glycol tri(meth)acrylates having 10 to 25 carbon atoms [e.g.diethylene glycol di(meth)acrylate, tripropylene glycoldi(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycoldi(meth)acrylate, 1,9-nonanediol di(meth)acrylate,3-methyl-1,5-pentanediol di(meth)acrylate,2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, pentaerythritoltri(meth)acrylate, modified bisphenol A di(meth)acrylate etc.],alicycle-containing di(meth)acrylates having 10 to 30 carbon atoms [e.g.dimethyloltricyclodecane di(meth)acrylate, tricyclodecanedimethanoldi(meth)acrylate etc.] and the like. These may be used alone, or two ormore may be used concurrently. Among them, from a view point thatcurability of the resin composition for a modeling material is improved,the polyfunctional ethylenic unsaturated monomer is preferablydiethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate,or modified bisphenol A di(meth)acrylate.

From a view point that curability of the resin composition for amodeling material is improved, the content of the polyfunctionalethylenic unsaturated monomer is preferably 70 parts by weight or less,and more preferably 60 parts by weight or less, based on 100 parts byweight of the whole resin composition for a modeling material.Additionally, the content of the polyfunctional ethylenic unsaturatedmonomer is preferably 20 parts by weight or more, and more preferably 30parts by weight or more, based on 100 parts by weight of the whole resincomposition for a modeling material. In addition, when two or more ofthe polyfunctional ethylenic unsaturated monomers are contained, thecontent is a total of the contents of respective polyfunctionalethylenic unsaturated monomers.

From a view point that curability of the resin composition for amodeling material is improved, the content of the (A) component ispreferably 80 parts by weight or more, and more preferably 90 parts byweight or more, based on 100 parts by weight of the whole resincomposition for a modeling material. Additionally, the content of the(A) component is preferably 99 parts by weight or less, and morepreferably 95 parts by weight or less. In addition, when two or more ofthe (A) components are contained, the content is a total of the contentsof respective (A) components.

<Photopolymerization Initiator (B)>

The photopolymerization initiator (B) is not particularly limited, asfar as it is a compound which promotes a radical reaction when light ofa wavelength in an ultraviolet ray, near ultraviolet ray or visiblelight region is irradiated. Examples of the (B) component include, forexample, benzoin compounds having 14 to 18 carbon atoms [e.g. benzoin,benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoinisobutyl ether etc.], acetophenone compounds having 8 to 18 carbon atoms[e.g. acetophenone, 2,2-diethoxy-2-phenylacetophenone,2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone,2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetophenone,1-hydroxycyclohexyl phenyl ketone,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one etc.],anthraquinone compounds having 14 to 19 carbon atoms [e.g.2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone,2-amylanthraquinone etc.], thioxanthone compounds having 13 to 17 carbonatoms [e.g. 2,4-diethylthioxanthone, 2-isopropylthioxanthone,2-chlorothioxanthone etc.], ketal compounds having 16 to 17 carbon atoms[e.g. acetophenonedimethylketal, benzyldimethylketal etc.], benzophenonecompounds having 13 to 21 carbon atoms [e.g. benzophenone,4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenoneetc.], acylphosphine oxide compounds having 22 to 28 carbon atoms [e.g.2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide,bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide], a mixture of thesecompounds and the like. These may be used alone, or two or more may beused concurrently. Among them, from a view point of light resistancethat a modeling material which is obtained by photocuring the resincomposition for a modeling material is yellowed with difficulty, the (B)component is preferably 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.Additionally, examples of an acylphosphine oxide compound which isavailable in the market include, for example, DAROCURE TPO manufacturedby BASF company and the like.

From a view point of photopolymerizability, the content of the (B)component is preferably 1 part by weight or more, and more preferably 3parts by weight or more, based on 100 parts by weight of the whole resincomposition for a modeling material. Additionally, the content of the(B) component is preferably 15 parts by weight or less, and morepreferably 13 parts by weight or less. In addition, when two or more ofthe (B) components are contained, the content is a total of the contentsof respective (B) components.

<Surface Adjusting Agent (C)>

The surface adjusting agent (C) is a component which adjusts the surfacetension of the resin composition at an appropriate range. Examples ofthe (C) component include, for example, a silicone-based compound andthe like. Examples of the silicone-based compound include, for example,a silicone-based compound having a polydimethylsiloxane structure, andthe like. Specifically, examples thereof include polyether-modifiedpolydimethylsiloxane, polyester-modified polydimethylsiloxane,polyaralkyl-modified polydimethylsiloxane and the like. As these,BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322,BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-344, BYK-370,BYK-375, BYK-377, BYK-UV3500, BYK-UV3510, BYK-UV3570 (forgoing aremanufactured by BYK-Chemie company), TEGO-Rad2100, TEGO-Rad2200N,TEGO-Rad2250, TEGO-Rad2300, TEGO-Rad2500, TEGO-Rad2600, TEGO-Rad2700(foregoing are manufactured by Degussa company), Granol 100, Granol 115,Granol 400, Granol 410, Granol 435, Granol 440, Granol 450, B-1484,Polyflow ATF-2, KL-600, UCR-L72, UCR-L93 (manufactured by KYOEISHACHEMICAL Co., LTD.) and the like as expressed by trade name may be used.These may be used alone, or two or more may be used concurrently.

From a view point that the surface tension of the resin composition isadjusted at an appropriate range, the content of the (C) component ispreferably 0.005 part by weight or more, and more preferably 0.01 partby weight or more, based on 100 parts by weight of the whole resincomposition for a modeling material. Additionally, the content of the(C) component is preferably 3.0 parts by weight or less, and morepreferably 1.5 parts by weight or less. In addition, when two or more ofthe (C) components are contained, the content is a total of the contentsof respective (C) components.

<(D) Oligomer>

It is preferable that the resin composition for a modeling material ofthe present embodiment further contains (D) an oligomer. The (D)component is a photocuring component having property that it cures byenergy rays. Examples of the (D) component include, for example, aurethane (meth)acrylate oligomer, an epoxy (meth)acrylate oligomer, apolyester (meth)acrylate oligomer, a polyether (meth)acrylate oligomerand the like. These may be used alone, or two or more may be usedconcurrently. Among them, from a view point that curability of the resincomposition for a modeling material is improved, the (D) component ispreferably a urethane (meth)acrylate oligomer.

From a view point that curability of the resin composition for amodeling material is improved, the content of the (D) component ispreferably 10 parts by weight or more, and more preferably 15 parts byweight or more, based on 100 parts by weight of the whole resincomposition for a modeling material. Additionally, the content of the(D) component is preferably 45 parts by weight or less, and morepreferably 40 parts by weight or less. In addition, when two or more ofthe (D) components are contained, the content is a total of the contentsof respective (D) components.

In addition, in the present description, the “oligomer” refers to onehaving a weight average molecular weight of 800 to 10,000. A weightaverage molecular weight means a weight average molecular weight interms of polystyrene, which is measured by GPC (Gel PermeationChromatography).

The resin composition for a modeling material can contain, as necessary,other additives in such a range that the effect of the present inventionis not impaired. Examples of other additives include, for example, anantioxidant, a coloring agent, a pigment dispersant, a preservationstabilizer, an ultraviolet absorbing agent, a light stabilizer, apolymerization inhibitor, a chain transfer agent, a filler and the like.

As the coloring agent, for example, the previously known coloring agentssuch as a diarylide-based coloring agent, a condensed azo-based coloringagent, a quinacridone-based coloring agent, a vat-based coloring agent,an isoindolinone-based coloring agent, a phthalocyanine-based coloringagent, an aniline-based coloring agent, titanium oxide, nickel titanium,yellow iron oxide, red iron oxide, ultramarine, cobalt blue, chromiumoxide, iron black, chrome yellow, chrome orange, molybdenum red, acadmium-based coloring agent, carbon black and the like can be used.These may be used alone, or two or more may be used concurrently. Amongthem, the coloring agent is preferably, for example, carbon black,Nickel Azo which is a condensed azo-based coloring agent, Quinacridonewhich is a quinacridone-based coloring agent, copper phthalocyaninewhich is a phthalocyanine-based coloring agent, titanium oxide or thelike. The content of the coloring agent is preferably 0.01 part byweight or more, and more preferably 0.1 part by weight or more, based on100 parts by weight of the whole resin composition for a modelingmaterial. Additionally, the content of the coloring agent is preferably5.0 parts by weight or less, and more preferably 3.0 parts by weight orless.

When a pigment is used as the coloring agent, the pigment dispersant maybe contained in order to improve dispersibility of the pigment. Examplesof the pigment dispersant include, for example, an ionic or nonionicsurfactant, an anionic, cationic or nonionic polymer compound and thelike. These may be used alone, or two more may be used concurrently.Among them, from respect of dispersion stability, the pigment dispersantis preferably a polymer compound comprising a cationic group or ananionic group. Examples of the pigment dispersant which is available inthe market include Solsperse manufactured by Avecia company, DISPERBYKmanufactured by BYK-Chemie company, EFKA manufactured by EFKA ADDITIVESB.V., and the like. The content of the pigment dispersant is preferably0.05 part by weight or more, based on 100 parts by weight of the wholeresin composition for a modeling material. Additionally, the content ofthe pigment dispersant is preferably 5 parts by weight or less.

The preservation stabilizer may be contained in order to enhancepreservation stability of the resin composition. Examples of thepreservation stabilizer include, for example, a hindered amine-basedcompound (HALS), a phenol-based antioxidant, a phosphorus-basedantioxidant and the like. Examples of the preservation stabilizerinclude specifically hydroquinone, methoquinone, benzoquinone,p-methoxyphenol, hydroquinone monomethyl ether, hydroquinone monobutylether, TEMPO, 4-hydroxy-TEMPO, TEMPOL, Cupherron AI, IRGASTAB UV-10,IRGASTAB UV-22, FIRSTCURE ST-1 (manufactured by ALBEMARLE company),t-butylcatechol, pyrogallol, TINUVIN 111 FDL, TINUVIN 144, TINUVIN 292,TINUVIN XP40, TINUVIN XP60, TINUVIN 400 manufactured by BASF company,and the like. These may be used alone, or two or more may be usedconcurrently.

The resin composition for a modeling material can be manufactured, forexample, by uniformly mixing the (A) to (C) components, and as necessary(D) oligomer and other additives using a mixing and stirring device orthe like, without particular limitation.

The thus manufactured resin composition for a modeling material haspreferably the viscosity at 25° C. of 70 mPa·s or less, from a viewpoint that dischargeability from an ink-jet head is improved. Inaddition, measurement of the viscosity of the resin composition for amodeling material is performed using a R100-type viscometer inaccordance with JIS Z 8803.

Additionally, the resin composition for a modeling material has thesurface tension Mt of 26.0 to 33.0 mN/m, from a view point thatdischargeability from an ink-jet head is improved. In addition, in thepresent description, the surface tension refers to a value of thesurface tension after 20 seconds from measurement initiation at 25° C.Measurement of the surface tension is performed, for example, using FullAutomatic Equilibrium Electro Surface Tension Meter ESB-V (manufacturedby Kyowa Interface Science Co., Ltd.).

Furthermore, the resin composition for a modeling material has surfacetension (also referred to as equivalence surface tension) Mstrepresented by the (i) expression, of 33.0 mN/m or more. When thesurface tension Mst is 33.0 mN/m or more, generation of bleeding at aninterface between the layer composed of the resin composition for amodeling material and the layer composed of the resin composition for asupporting material can be suppressed. That is, by movement of the resincomposition for a modeling material to a side of the resin compositionfor a supporting material, or by movement of the resin composition for asupporting material to a side of the resin composition for a modelingmaterial, phenomenon of generation of blur becomes difficult to begenerated. As a result, a light cured article having the gooddimensional accuracy can be obtained using a light curing molding inkset comprising a combination of such resin composition for a modelingmaterial and resin composition for a supporting material. Additionally,the surface tension Mst is preferably 40.0 mN/m or less, and morepreferably 39.0 mN/m or less.

In addition, the photocuring component in the expression is a componenthaving property that it cures by energy rays. In the resin compositionfor a modeling material of the present embodiment, the (A) ethylenicunsaturated monomer, and the (D) oligomer which is an optional componentare the photocuring component. The resin composition for a modelingmaterial of the present embodiment may comprise other photocuringcomponents.

2. Resin Composition for Supporting Material

It is preferable that the resin composition for a supporting materialcontains a water-soluble monofunctional ethylenic unsaturated monomer(E), polyalkylene glycol comprising an oxyethylene group and/or anoxypropylene group (F), a photopolymerization initiator (B), and asurface adjusting agent (C).

<(E) Water-Soluble Monofunctional Ethylenic Unsaturated Monomer>

As the (E) water-soluble monofunctional ethylenic unsaturated monomer,the same components as those of the resin composition for a modelingmaterial can be used.

From a view point that curability of the resin composition for asupporting material is improved, and a supporting material which isobtained by photocuring the resin composition for a supporting materialis rapidly dissolved in water, the content of the (E) component ispreferably 20 parts by weight or more, and more preferably 25 parts byweight or more, based on 100 parts by weight of the whole resincomposition for a supporting material. Additionally, the content of the(E) component is preferably 50 parts by weight or less, and morepreferably 45 parts by weight or less. In addition, when two or more ofthe (E) components are contained, the content is a total of the contentsof respective (E) components.

<Polyalkylene Glycol Comprising Oxyethylene Group and/or OxypropyleneGroup (F)>

The polyalkylene glycol comprising an oxyethylene group and/or anoxypropylene group (F) is such that at least ethylene oxide and/orpropylene oxide are (is) added to an active hydrogen compound. Examplesof the (F) component include, for example, polyethylene glycol,polypropylene glycol and the like. These may be used alone, or two ormore may be used concurrently. Examples of the active hydrogen compoundinclude monohydric to tetrahydric alcohols, amine compounds and thelike. Among them, the active hydrogen compound is preferably a dihydricalcohol or water.

From a view point that solubility in water of a supporting materialwhich is obtained by photocuring the resin composition for a supportingmaterial is enhanced, the content of the (F) component is preferably 20parts by weight or more, and more preferably 25 parts by weight or more,based on 100 parts by weight of the whole resin composition for asupporting material. Additionally, the content of the (F) component ispreferably 49 parts by weight or less, and more preferably 45 parts byweight or less. In addition, when two or more of the (F) components arecontained, the content is a total of the contents of respective (F)components.

A number average molecular weight Mn of the (F) component is preferably100 to 5,000. When Mn of the (F) component is in the range, the resincomposition is compatible with the (F) component before photocuring, andis not compatible with the (F) component after photocuring. As a result,self-standing of a supporting material which is obtained by photocuringthe resin composition for a supporting material can be enhanced, andsolubility of the supporting material in water can be enhanced. Mn ofthe (F) component is more preferably 200 to 3,000, and furtherpreferably 400 to 2,000.

<Photopolymerization Initiator (B)>

<Surface Adjusting Agent (C)>

As the photopolymerization initiator (B) and the surface adjusting agent(C), the same components as those of the resin composition for amodeling material can be used at the same contents.

The resin composition for a supporting material can contain otheradditives, as necessary, in such a range that the effect of the presentinvention is not impaired. Examples of other additives include, forexample, a water-soluble organic solvent, an antioxidant, a coloringagent, a pigment dispersant, a preservation stabilizer, an ultravioletabsorbing agent, a light stabilizer, a polymerization inhibitor, a chaintransfer agent, a filler and the like.

Examples of the water-soluble organic solvent include, for example,ethylene glycol monoacetate, propylene glycol monoacetate, diethyleneglycol monoacetate, dipropylene glycol monoacetate, triethylene glycolmonoacetate, tripropylene glycol monoacetate, tetraethylene glycolmonoacetate, tetrapropylene glycol monoacetate, ethylene glycolmonomethyl ether, propylene glycol monomethyl ether, diethylene glycolmonomethyl ether, dipropylene glycol monomethyl ether, triethyleneglycol monomethyl ether, tripropylene glycol monomethyl ether,tetraethylene glycol monomethyl ether, tetrapropylene glycol monomethylether, ethylene glycol monoethyl ether, propylene glycol monoethylether, diethylene glycol monoethyl ether, dipropylene glycol monoethylether, triethylene glycol monoethyl ether, tripropylene glycol monoethylether, tetraethylene glycol monoethyl ether, tetrapropylene glycolmonoethyl ether, ethylene glycol monopropyl ether, propylene glycolmonopropyl ether, diethylene glycol monopropyl ether, dipropylene glycolmonopropyl ether, triethylene glycol monopropyl ether, tripropyleneglycol monopropyl ether, tetraethylene glycol monopropyl ether,tetraethylene glycol monopropyl ether, ethylene glycol monobutyl ether,propylene glycol monobutyl ether, diethylene glycol monobutyl ether,dipropylene glycol monobutyl ether, triethylene glycol monobutyl ether,tripropylene glycol monobutyl ether, tetraethylene glycol monobutylether, tetrapropylene glycol monobutyl ether, ethylene glycol diacetate,propylene glycol diacetate, diethylene glycol diacetate, dipropyleneglycol diacetate, triethylene glycol diacetate, tripropylene glycoldiacetate, tetraethylene glycol diacetate, tetrapropylene glycoldiacetate, ethylene glycol dimethyl ether, propylene glycol dimethylether, diethylene glycol dimethyl ether, dipropylene glycol dimethylether, triethylene glycol dimethyl ether, tripropylene glycol dimethylether, tetraethylene glycol dimethyl ether, tetrapropylene glycoldimethyl ether, ethylene glycol diethyl ether, propylene glycol diethylether, diethylene glycol diethyl ether, dipropylene glycol diethylether, triethylene glycol diethyl ether, tripropylene glycol diethylether, tetraethylene glycol diethyl ether, tetrapropylene glycol diethylether, ethylene glycol dipropyl ether, propylene glycol dipropyl ether,diethylene glycol dipropyl ether, dipropylene glycol dipropyl ether,triethylene glycol dipropyl ether, tripropylene glycol dipropyl ether,tetraethylene glycol dipropyl ether, tetrapropylene glycol dipropylether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether,diethylene glycol dibutyl ether, dipropylene glycol dibutyl ether,triethylene glycol dibutyl ether, tripropylene glycol dibutyl ether,tetraethylene glycol dibutyl ether, tetrapropylene glycol dibutyl ether,ethylene glycol monomethyl ether acetate, propylene glycol monomethylether acetate, diethylene glycol monomethyl ether acetate, dipropyleneglycol monomethyl ether acetate, triethylene glycol monomethyl etheracetate, tripropylene glycol monomethyl ether acetate, tetraethyleneglycol monomethyl ether acetate, tetrapropylene glycol monomethyl etheracetate, ethylene glycol monoethyl ether acetate, propylene glycolmonoethyl ether acetate, diethylene glycol monoethyl ether acetate,dipropylene glycol monoethyl ether acetate, triethylene glycol monoethylether acetate, tripropylene glycol monoethyl ether acetate,tetraethylene glycol monoethyl ether acetate, tetrapropylene glycolmonoethyl ether acetate, ethylene glycol monopropyl ether acetate,propylene glycol monopropyl ether acetate, diethylene glycol monopropylether acetate, dipropylene glycol monopropyl ether acetate, triethyleneglycol monopropyl ether acetate, tripropylene glycol monopropyl etheracetate, tetraethylene glycol monopropyl ether acetate, tetrapropyleneglycol monopropyl ether acetate, ethylene glycol monobutyl etheracetate, propylene glycol monobutyl ether acetate, diethylene glycolmonobutyl ether acetate, dipropylene glycol monobutyl ether acetate,triethylene glycol monobutyl ether acetate, tripropylene glycolmonobutyl ether acetate, tetraethylene glycol monobutyl ether acetate,tetrapropylene glycol monobutyl ether acetate and the like. These may beused alone, or two or more may be used concurrently. From a view pointthat solubility of the supporting material in water is improved, and theresin composition for a supporting material is adjusted at the lowviscosity, among them, the water-soluble organic solvent is morepreferably triethylene glycol monomethyl ether, or dipropylene glycolmonomethyl ether acetate.

From a view point that solubility of the supporting material in water isimproved, and the resin composition for a supporting material isadjusted at the low viscosity, the content of the water-soluble organicsolvent is preferably 5 parts by weight or more, and more preferably 10parts by weight or more, based on 100 parts by weight of the whole resincomposition for a supporting material. Additionally, the content of thewater-soluble organic solvent is preferably 35 parts by weight or less,and more preferably 30 parts by weight or less. In addition, when two ormore of the water-soluble organic solvents are contained, the content isa total of the contents of respective water-soluble organic solvents.

As the coloring agent, the pigment dispersant, and the preservationstabilizer, the same components as those of the resin-composition for amodeling material can be used at the same contents.

A method for manufacturing the resin composition for a supportingmaterial is not particularly limited. The resin composition for asupporting material can be manufactured, for example, by uniformlymixing the (B), (C), (E), and (F) components, and as necessary, otheradditives using a mixing and stirring device or the like.

From a view point that dischargeability from an ink-jet head isimproved, the thus manufactured resin composition for a supportingmaterial has preferably the viscosity at 25° C. of 70 mPa·s or less. Inaddition, measurement of the viscosity of the resin composition for asupporting material is performed using a R100-type viscometer inaccordance with JIS Z 8803.

Additionally, from a view point that dischargeability from an ink-jethead is improved, the resin composition for a supporting material haspreferably the surface tension of 24.0 to 33.0 mN/m. In addition, in thepresent description, the surface tension refers to a value of thesurface tension after 20 seconds from measurement initiation at 25° C.Measurement of the surface tension is performed, for example, using FullAutomatic Equilibrium Electro Surface Tension Meter ESB-V (manufacturedby Kyowa Interface Science Co., Ltd.).

3. Optically Shaped Article and Manufacturing Method Thereof

The light cured article is manufactured using the resin composition fora modeling material and the light curing molding ink set comprising theresin composition for a modeling material, of the present embodiment bya manufacturing method for light curing molding using an ink-jet scheme.Specifically, the light cured article is manufactured by passing througha step (I) of discharging a resin composition for a modeling materialand a resin composition for a supporting material from an ink-jet headso that a resin composition layer in which a layer composed of the resincomposition for a modeling material and a layer composed of the resincomposition for a supporting material are arranged contiguously isformed, a step (II) of photocuring the resin composition for a modelingmaterial and the resin composition for a supporting materialconstituting the resin composition layer, respectively, thereby,obtaining a modeling material and a supporting material, and a step(III) of removing the supporting material, thereby, obtaining a lightcured article. The steps (I) to (III) are not particularly limited, butare performed, for example, by the following method.

<Step (I)>

FIG. 1 is a view schematically showing a step (I) in the method formanufacturing a light cured article of the present embodiment. As shownin FIG. 1, a three-dimensional shaping apparatus 1 comprises an ink-jethead module 2 and a shaping table 3. The ink-jet head module 2 has alight curing molding ink unit 25, a roller 23, and a light source 24.The light curing molding ink unit 25 has an ink-jet head 21 for amodeling material, which is filled with a resin composition 4 a for amodeling material, and an ink-jet head 22 for a supporting material,which is filled with a resin composition 5 a for, a supporting material.In addition, the light curing molding ink set 20 of the presentembodiment is constructed of a combination of the resin composition 4 afor a modeling material and the resin composition 5 a for a supportingmaterial.

First, the ink-jet head module 2 is made to perform scanning in an Xdirection and a Y direction, and at the same time, discharge the resincomposition 4 a for a modeling material from the ink-jet head 21 for amodeling material, and discharge the resin composition 5 a for asupporting material from the ink-jet head 22 for a supporting material,relatively to the shaping table 3 in FIG. 1. Thereby, a resincomposition layer in which interfaces between a layer composed of theresin composition 4 a for a modeling material and a layer composed ofthe resin composition 5 a for a supporting material are arrangedcontiguously so as to come into contact with each other is formed on theshaping table 3. And, in order to smooth an upper surface of the resincomposition layer, the extra resin composition 4 a for a modelingmaterial and resin composition 5 a for a supporting material are removedusing the roller 23.

<Step (II)>

FIG. 2 is a view schematically showing a step (II) in the method formanufacturing a light cured article of the present embodiment. As shownin FIG. 2, by irradiating light to the resin composition layer which hasbeen formed by a step (I), using the light source 24, a cured layercomposed of a modeling material 4 and a supporting material 5 is formed.

Then, the shaping table 3 is lowered in a Z direction in FIG. 1 by athickness of the cured layer. Thereafter, by the same methods as thoseof the steps (I) and (II), on the cured layer, a cured layer composed ofa modeling material 4 and a supporting material 5 is further formed. Byperforming these steps repeatedly, a cured product 6 composed of themodeling material 4 and the supporting material 5 is made. FIG. 3 is aview schematically showing a cured product 6 composed of a modelingmaterial 4 and a supporting material 5, which has been obtained byrepeatedly performing steps (I) and (II) in the method for manufacturinga light cured article of the present embodiment.

Examples of light which cures the resin composition include, forexample, far infrared rays, infrared rays, visible rays, nearultraviolet rays, ultraviolet rays and the like. Among them, from a viewpoint of easiness and the efficiency of curing work, near ultravioletrays or ultraviolet rays are preferable.

Examples of the light source 24 include a mercury lamp, a metal halidelamp, an ultraviolet. LED, an ultraviolet laser and the like. Amongthem, from a view point of miniaturization of facilities and electricpower saving, the light source 24 is preferably an ultraviolet LED. Inaddition, when the ultraviolet LED is used as the light source 24, theintegrated light quantity of ultraviolet rays is preferably around 500mJ/cm².

<Step (III)>

FIG. 4 is a view schematically showing a step (III) in the method formanufacturing a light cured article of the present embodiment. As shownin FIG. 4, the cured product 6 composed of the modeling material 4 andthe supporting material 5, which has been made in a step (III), isimmersed in a solvent 8 contained in a container 7. Thereby, thesupporting material 5 can be removed by dissolving it in the solvent 8.

Examples of the solvent 8 which dissolves the supporting material 5include, for example, ion-exchanged water, distilled water, tap water,well water and the like. Among them, from a view point of relatively fewimpurities and availability at a low price, the solvent 8 is preferablyion-exchanged water.

By the forgoing steps, a light cured article having the good dimensionalaccuracy can be obtained using the resin composition for a modelingmaterial and the light curing molding ink set of the present embodiment.

Examples which disclose the present embodiment more specifically will beshown below. In addition, the present invention is not limited to onlythese Examples.

Examples

[Assessment of Relevancy Between Dimensional Accuracy and Bleeding]

<Method of Assessing. Dimensional Accuracy>

Using each resin composition for a modeling material and each resincomposition for a supporting material of test Nos. A1 to A4 shown inTable 1, a cured product was made. A shape and a target dimension of thecured product are shown in FIGS. 5 (a) and (b). In addition, a step ofdischarging each resin composition for a modeling material and eachresin composition for a supporting material from an ink-jet head wasperformed so that the resolution became 600×600 dpi, and a thickness ofone resin composition layer became 48 μm. Additionally, a step ofphotocuring each resin composition for a modeling material and eachresin composition for a supporting material, respectively, was performedusing a LED light source of a wavelength 385 nm, which had beeninstalled on a rear side of an ink-jet head in a scanning direction,under the conditions of the illuminance of 580 mW/cm², and theintegrated light quantity per one resin composition layer of 600 mJ/cm².Then, by immersing the cured product in ion-exchanged water, thesupporting material was removed to obtain a light cured article.Thereafter, the resulting light cured article was allowed to stand in adesiccator for 24 hours, and was sufficiently dried. By theabove-mentioned step, each five of light cured articles of test Nos. A1to A4 were manufactured. Concerning the light cured articles afterdrying, dimensions in an x direction and a y direction in FIG. 5 (a)were measured using a slide caliper, and a change rate from the targetdimension was calculated. For the dimensional accuracy, an average of adimensional change rate in respective light cured articles of test Nos.A1 to A4 was obtained, and assessment was performed using the averagebased on the following criteria. The assessment results are shown inTable 1.

O: An average dimensional change rate is less than ±1.0%.

x: An average dimensional change rate is ±1.0% or more.

<Method of Assessing Bleeding>

First, each 0.02 mL of each resin composition for a modeling materialand each resin composition for a supporting material shown in Table 1were added dropwise on a film composed of polyethylene terephthalate(A4300, manufactured by TOYOBO CO., LTD., 100 mm×150 mm×thickness 188μm) using a micropipette. Thereupon, in the resin composition for amodeling material and the resin composition for a supporting material, adistance between central parts of respective liquid droplets was 10 mm,and respective liquid droplets were independent. Thereafter, respectiveliquid droplets were gradually wettedly spread, and respective liquiddroplets were unified after about 10 seconds. Thereupon, the state of aninterface of respective liquid droplets was observed visually from anupper side, and bleeding was assessed based on the following criteria.The assessment results are shown in Table 1.

O: An interface between a layer composed of a resin composition for amodeling material and a layer composed of a resin composition for asupporting material became linear when viewed from the top, and bleedingwas not generated.

Δ: At an interface between a layer composed of a resin composition for amodeling material and a layer composed of a resin composition for asupporting material, slight bleeding was generated.

x: At an interface between a layer composed of a resin composition for amodeling material and a layer composed of a resin composition for asupporting material, bleeding was generated.

TABLE 1 Resin Resin Dimensional composition composition accuracy Testfor modeling for supporting x di- y di- Bleeding No. material materialrection rection assessment A1 MTD-23 STD-9 X X X A2 STD-11 ◯ ◯ ◯ A3MTD-25 STD-9 X X X A4 STD-11 ◯ ◯ ◯

As seen from the results of Table 1, in the light cured articles of testNos. A2 and A4, which had the good dimensional accuracy, an interfacebetween the layer composed of the resin composition for a modelingmaterial and the layer composed of the resin composition for asupporting material became linear, and bleeding was not generated. Onthe other hand, in the light cured articles of test Nos. A1 and A3, thedimensional accuracy of which had reduced, by movement of the resincomposition for a modeling material to a side of the resin compositionfor a supporting material, at an interface between the layer composed ofthe resin composition for a modeling material and the layer composed ofthe resin composition for a supporting material, bleeding was generated.In this way, bleeding which is generated at an interface between thelayer composed of the resin composition for a modeling material and thelayer composed of the resin composition for a supporting material is oneof the causes for reduction in the dimensional accuracy of the lightcured article. Then, bleeding which is generated at an interface betweenthe layer composed of the resin composition for a modeling material andthe layer composed of the resin composition for a supporting materialwas assessed below.

[Assessment of Bleeding]

<Adjustment of Resin Composition>

(Preparation of Resin Composition for Model Material)

According to formulation shown in Table 2, (A) to (D) components, andother additives were uniformly mixed using a mixing and stirring device,and resin compositions for a modeling material of M1 to M23 weremanufactured.

TABLE 2 Surface tension Resin composition for modeling material (mN/m)M1 M2 M3 M4 M5 M6 M7 M8 Formulation (A) Monofunctional ethylenic BCHA28.5 — — — — — — — 68.8 (part by weight) unsaturated monomer TMCHA 27.368.8 58.8 48.8 38.8 28.8 18.8 8.8 — ACMO 44.6 — — — — — — — — PEA 39.2 —10.0 20.0 30.0 40.0 50.0 60.0 — Polyfunctional ethylenic DEGDA 38.2 — —— — — — — — unsaturated monomer A-NPA 32.0 — — — — — — — — Ebe150 38.6 —— — — — — — 25 (B) Photopolymerization DAROCURE — 5 5 5 5 5 5 5 5initiator TPO IRGACURE907 — — — — — — — — — Chivacure ITX — — — — — — —— — (C) Surface adjusting agent BYK-UV3500 — 0.01 0.01 0.01 0.01 0.010.01 0.01 0.01 (D) Oligomer CN996 39.6 25 25 25 25 25 25 25 — OtherColoring agent MA-8 — — — — — — — — — additives Yellow G01 — — — — — — —— — RT355D — — — — — — — — — BT-617-D — — — — — — — — — CR-60 — 1.001.00 1.00 1.00 1.00 1.00 1.00 1.00 Pigment diapersant Sol.32000 — 0.200.20 0.20 0.20 0.20 0.20 0.20 0.20 Surface tension (mN/m) Mt 25.2* 25.7*26.6 28.1 29.4 30.6 32.5 25.0* Mst 30.6* 31.8* 33.1 34.4 35.7 36.9 38.231.2* Discharge stability Nozzle slip-out Δ Δ ∘ ∘ ∘ ∘ ∘ Δ Ligamentlength ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Surface tension Resin composition for modelingmaterial (mN/m) M9 M10 M11 M12 M13 M14 M15 M16 Formulation (A)Monofunctional ethylenic BCHA 28.5 58.8 48.8 38.8 28.8 18.8 8.8 — —(part by weight) unsaturated monomer TMCHA 27.3 — — — — — — — — ACMO44.6 — — — — — — 38.8 — PEA 39.2 — — — — — — — 38.8 Polyfunctionalethylenic DEGDA 38.2 10 20 30 40 50 60 30 — unsaturated monomer A-NPA32.0 — — — — — — — 30 Ebe150 38.6 25 25 25 25 25 25 25 25 (B)Photopolymerization DAROCURE — 5 5 5 5 5 5 5 — initiator TPO IRGACURE907— — — — — — — — 45 Chivacure ITX — — — — — — — — 0.5 (C) Surfaceadjusting agent BYK-UV3500 — 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 (D)Oligomer CN996 39.6 — — — — — — — — Other Coloring agent MA-8 — — — — —— — — — additives Yellow G01 — — — — — — — — — RT355D — — — — — — — — —BT-617-D — — — — — — — — — CR-60 — 1.00 1.00 1.00 1.00 1.00 1.00 1.001.00 Pigment diapersant Sol.32000 — 0.20 0.20 0.20 0.20 0.20 0.20 0.200.20 Surface tension (mN/m) Mt 25.2* 25.6* 26.2 27.9 29.5 31.8 32.1 29.4Mst 32.2* 33.3 34.3 35.3 36.4 37.4 38.4 36.7 Discharge stability Nozzleslip-out Δ Δ ∘ ∘ ∘ ∘ ∘ ∘ Ligament length ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Surface tensionResin composition for modeling material (mN/m) M17 M18 M19 M20 M21 M22M23 Formulation (A) Monofunctional ethylenic BCHA 28.5 — — — — — — —(part by weight) unsaturated monomer TMCHA 27.3 39.2 39.2 39.2 39.2 40.028.8 28.8 ACMO 44.6 — — — — — — — PEA 39.2 30.0 30.0 30.0 30.0 30.0 40.040.0 Polyfunctional ethylenic DEGDA 38.2 — — — — — — — unsaturatedmonomer A-NPA 32.0 — — — — — — — Ebe150 38.6 — — — — — — — (B)Photopolymerization DAROCURE — 5 5 5 5 5 5 5 initiator TPO IRGACURE907 —— — — — — — — Chivacure ITX — — — — — — — — (C) Surface adjusting agentBYK-UV3500 — 0.01 0.01 0.01 0.01 0.01 — 0 (D) Oligomer CN996 39.6 25 2525 25 25 25 25 Other Coloring agent MA-8 — 0.50 — — — — — — additivesYellow G01 — — 050 — — — — — RT355D — — — 0.50 — — — — BT-617-D — — — —0.50 — — — CR-60 — — — — — — 1.00 1.00 Pigment diapersant Sol.32000 —0.25 0.25 0.25 0.25 — 0.20 0.20 Surface tension (mN/m) Mt 27.8 28.4 27.927.6 28.4 36.1* 23.8* Mst 34.4 34.4 34.4 34.4 34.3 36.3 36.3 Dischargestability Nozzle slip-out ∘ ∘ ∘ ∘ ∘ ∘ x Ligament length ∘ ∘ ∘ ∘ ∘ x ∘*means outside a range defined in claim 1.

BCHA: 4-t-Butylcyclohexanol acrylate [SR217 (ethylenic double bond/onemolecule: one), manufactured by Arkema S.A.]

TMCHA: 3,3,5-Trimethylcyclohexanol acrylate [SR420 (ethylenic doublebond/one molecule: one), manufactured by Arkema S.A.]

ACMO: Acryloylmorpholine [ACMO (ethylenic double bond/one molecule:one), manufactured by KJ Chemicals Corporation]

PEA: Phenoxyethyl acrylate [SR339 (ethylenic double bond/one molecule:one), manufactured by Arkema S.A.]

DEGDA: Diethylene glycol diacrylate [SR230 (ethylenic double bond/onemolecule: 2), manufactured by Arkema S.A.]

A-NPA: Alkoxylated neopentyl glycol diacrylate [SR9003 (ethylenic doublebond/one molecule: 2), manufactured by Arkema S.A.]

Ebe150: Modified bisphenol A diacrylate [Ebacryl150 (ethylenic doublebond/one molecule: 2), manufactured by DAICEL-ALLNEX LTD.]

DAROCURE TPO: 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide [DAROCURETPO, manufactured by BASF company]

IRGACURE907: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one[IRGACURE 907, manufactured by Ciba company]

Chivacure ITX: 2-Isopropylthioxanthone [Chivacure ITX, manufactured byDouble Bond Chemical Co., Ltd.]

BYK-UV3500: Silicone-based compound having a polydimethylsiloxanestructure [BYK-UV3500, manufactured by BYK-Chemie company]

CN996: Urethane acrylate oligomer [CN996 (ethylenic double bond/onemolecule: 2), manufactured by Arkema S.A.]

MA-8: Acidic carbon black pigment [MA-8, manufactured by MitsubishiChemical Corporation]

Yellow G01: Nickel azo pigment [Yellow G01, manufactured by Levascreencompany]

RT355D: Quinacridone pigment [CINQUASIA Magenda RT-355-D, manufacturedby Ciba company]

BT-617-D: Copper phthalocyanine pigment [HOSTAPERM BLUE BT-617-D,manufactured by Clariant company]

CR-60: Titanium oxide [CR-60, manufactured by ISHIHARA SANGYO KAISHA,LTD.]

Sol. 32000: Comb-type copolymer having a basic functional group[Solsperse 32000, manufactured by Avecia company]

(Preparation of Resin Composition for Support Material)

According to formulation shown in Table 3, (B), (C), (E), and (F)components, and a water-soluble organic solvent were uniformly mixedusing a mixing and stirring device, and resin compositions for asupporting material of S1 to S6 were manufactured.

TABLE 3 Resin composition for supporting material S1 S2 S3 S4 S5 S6Formulation (E) Water-soluble monofunctional ACMO 50.0 49.9 49.7 29.249.5 49.0  (part by weight) ethylenic unsaturated monomer (F)Polyalkylene glycol comprising PPG-1000 45.0 45.0 45.0 30.0 45.0 45.0 oxyethylene group and/or oxypropylene group (B) Photopolymerizationinitiator DAROCURE TPO  5.0  5.0  5.0 5.0  5.0 5.0 IRGACURE907 — — — 5.0— — Chivacure ITX — — — 0.5 — — (C) Surface adjusting agent BYK-307 — 0.1  0.3 0.3  0.5 1.0 Other Water-soluble organic solvent MTG — — —30.0 — — additives Surface tension (mN/m) St  40.1**  35.2** 32.7 32.225.1  23.4** Discharge stability Nozzle slip-out ∘ ∘ ∘ ∘ ∘ x Ligamentlength x Δ ∘ ∘ ∘ ∘ **means outside a range defined in claim 6.

ACMO: Acryloylmorpholine [ACMO (ethylenic double bond/one molecule:one), manufactured by KJ Chemicals Corporation]

PPG-1000: Polypropylene glycol [UNIOL D1000 (molecular weight 1000),manufactured by NOF CORPORATION]

DAROCURE TPO: 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide [DEROCURETPO, manufactured by BASF company]

IRGACURE907:2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopro pane-1-one[IRGACURE 907, manufactured by Ciba company]

Chivacure ITX: Isopropylthioxanthone [Chivacure ITX, manufactured byDouble Bond Chemical Ind., Co., Ltd.]

BYK-307: Silicone-based compound having a polydimethylcyclohexanestructure [BYK-307, manufactured by BYK-Chemie company]

MTG: Triethylene glycol monomethyl ether [MPG, manufactured by NIPPONNYUKAZAI CO., LTD.]

<Method of Measuring Surface Tension>

As the surface tension of each resin composition for a modeling materialof M1 to M23 and each photocuring component contained in the resincomposition for a modeling material shown in Table 2, as well as eachresin composition for a supporting material of S1 to S6 and eachphotocuring component contained in the resin composition for asupporting material shown in Table 3, a value after 20 seconds frommeasurement initiation, at 25° C. was measured using Full AutomaticEquilibrium Electro Surface Tension Meter ESB-V (manufactured by KyowaInterface Science Co., Ltd.). The measurement results are shown in Table2 and Table 3.

<Method of Assessing Discharge Stability>

Discharge stability of each composition for a modeling material of M1 toM23 shown in Table 2 and each resin composition for a supportingmaterial of S1 to S6 shown in Table 3 was assessed by calculating theratio of generation of nozzle slip-out, and the ligament length.

(Ratio of Generation of Nozzle Slip-Out)

By performing continuous discharge under the conditions of a nozzlediameter: 20 μm, a flying speed: 7 m/sec, a discharge frequency: 10 kHz,and a continuous discharge time: 5 min, a nozzle check pattern wasprinted, and the number of nozzles in which nozzle slip-out wasgenerated was counted. And, the ratio of generation of nozzle slip-outwas assessed based on the following criteria. The assessment results areshown in Table 2 and Table 3. In addition, nozzle slip-out refers to thestate where an ink is not discharged due to clogging of a nozzle.

O: Nozzle slip-out 0%

Δ: Nozzle slip-out more than 0% to less than 5%

x: Nozzle slip-out 5% or more

(Ligament Length)

Discharge was performed under the conditions of a nozzle diameter: 20μm, a flying speed: 7 m/sec. and a discharge frequency: 1 kHz, the timefrom passing of the head of liquid droplets until passing of the tailend of liquid droplets was measured at a position of 1 mm distance fromthe nozzle, and thereafter, the ligament length was calculated byintegrating the time and the flying speed. And, the ligament length wasassessed based on the following criteria. The assessment results areshown in Table 2 and Table 3. In addition, the ligament length refers tothe length of a liquid droplet which is discharged from a nozzle. Whenthe ligament length is great, ink mist becomes easy to be generated.

O: Ligament length less than 300 μm

Δ: Ligament length 300 to 500 μm

x: Ligament length more than 500 μm

In addition, in the present description, the resin composition in whichassessment of the ratio of generation of nozzle slip-out was “O”, andassessment of the ligament length was “O” was determined to be excellentin discharge stability. Additionally, the resin composition havinganother assessment was determined to be inferior in discharge stability.

As seen from Table 2, resin compositions for a modeling material of M3to M7, and M11 to M21 in which the surface tension Mt is 26.0 to 33.0mN/m are excellent in discharge stability. Additionally, as seen fromTable 3, resin compositions for a supporting material of S3 to S5 inwhich the surface tension St is 24.0 to 33.0 mN/m are excellent indischarge stability.

<Method of Assessing Bleeding>

Using each resin composition for a modeling material of M1 to M21 shownin Table 2 and each resin composition for a supporting material of S3and S4 shown in Table 3, bleeding was assessed by the same method asthat described above. The assessment results are shown in Table 4 andTable 5.

TABLE 4 Resin composition for Resin composition for Bleeding Test No.modeling material supporting material assessment 1 M1* S3 X 2 M2* X 3 M3◯ 4 M4 ◯ 5 M5 ◯ 6 M6 ◯ 7 M7 ◯ 8 M8* X 9 M9* X 10 M10* Δ 11 M11 ◯ 12 M12◯ 13 M13 ◯ 14 M14 ◯ 15 M15 ◯ 16 M16 ◯ 17 M1* S4 X 18 M2* X 19 M3 ◯ 20 M4◯ 21 M5 ◯ 22 M6 ◯ 23 M7 ◯ 24 M8* X 25 M9* X 26 M10* Δ 27 M11 ◯ 28 M12 ◯29 M13 ◯ 30 M14 ◯ 31 M15 ◯ 32 M16 ◯ *means outside a range defined inclaim 1.

TABLE 5 Resin composition for Resin composition for Bleeding Test No.modeling material supporting material assessment 33 M17 S3 ◯ 34 S4 ◯ 35M18 S3 ◯ 36 S4 ◯ 37 M19 S3 ◯ 38 S4 ◯ 39 M20 S3 ◯ 40 S4 ◯ 41 M4 S3 ◯ 42S4 ◯ 43 M21 S3 ◯ 44 S4 ◯

As seen from the results of Table 4, in the resin compositions for amodeling material and the resin compositions for a supporting materialof test Nos. 3 to 7, 11 to 16, 19 to 23, and 27 to 32 satisfying allrequirements of the present invention, an interface between the layercomposed of the resin composition for a modeling material and the layercomposed of the resin composition for a supporting material becamelinier when viewed from the top, and bleeding was not generated.

On the other hand, in the resin compositions for a modeling material andthe resin compositions for a supporting material of test Nos. 1, 2, 8,9, 17, 18, 24 and 25, in which the surface tension Mt and the surfacetension Mst represented by the (i) expression do not satisfy therequirements of the present invention, at an interface between the layercomposed of the resin composition for a modeling material and the layercomposed of the resin composition for a supporting material, blur wasgenerated.

Additionally, in the resin compositions for a modeling material and theresin compositions for a supporting material of test Nos. 10 and 26, thesurface tension Mt of which does not satisfy the requirement of thepresent invention, at an interface between the layer composed of theresin composition for a modeling material and the layer composed of theresin composition for a supporting material, slight blur was generated.

As seen from the results of Table 5, in the resin compositions for amodeling material and the resin compositions for a supporting materialof test Nos. 33 to 44 satisfying all requirements of the presentinvention, an interface between the layer composed of the resincomposition for a modeling material and the layer composed of the resincomposition for a supporting material became linier, and bleeding wasnot generated. That is, in the resin compositions for a modelingmaterial and the resin compositions for a supporting material satisfyingall requirements of the present invention, even when the coloring agentis not contained, or a kind of the coloring agent was changed, bleedingis not generated.

As shown in Table 1, when bleeding is not generated at an interfacebetween the layer composed of the resin composition for a modelingmaterial and the layer composed of the resin composition for asupporting material, a light cured article having the good dimensionalaccuracy is obtained. On the other hand, when bleeding is generated atan interface between the layer composed of the resin composition for amodeling material and the layer composed of the resin composition for asupporting material, the dimensional accuracy of a light cured articleis reduced. Accordingly, since in the resin compositions for a modelingmaterial and the resin compositions for a supporting material of testNos. 3 to 7, 11 to 16, 19 to 23, 27 to 32, and 33 to 44 satisfying allrequirements of the present invention, at an interface between the layercomposed of the resin composition for a modeling material and the layercomposed of the resin composition for a supporting material, bleedingwas not generated, a light cured article having the good dimensionalaccuracy is obtained. On the other hand, since in the resin compositionsfor a modeling material and the resin compositions for a supportingmaterial of test Nos. 1, 2, 8, 9, 10, 17, 18, and 24 to 26 notsatisfying the requirements of the present invention, at an interfacebetween the layer composed of the resin composition for a modelingmaterial and the layer composed of the resin composition for asupporting material, bleeding was generated, the dimensional accuracy ofa light cured article is reduced.

OTHER EMBODIMENTS

The method for manufacturing a light cured article of theabove-mentioned embodiment may further comprise a step of dischargingonly a resin composition for a modeling material from an ink-jet head sothat only a layer composed of the resin composition for a modelingmaterial is formed, thereafter, photocuring the resin composition for amodeling material constituting the layer, thereby, obtaining a modelingmaterial and/or a step of discharging only a resin composition for asupporting material from an ink-jet head so that only a layer composedof the resin composition for a supporting material is formed,thereafter, photocuring the resin composition for a supporting materialconstituting the layer, thereby, obtaining a supporting material.

INDUSTRIAL APPLICABILITY

The resin composition for a modeling material, and the light curingmolding ink set comprising the resin composition for a modeling materialof the present invention can afford a light cured article having thegood dimensional accuracy. Hence, the resin composition for a modelingmaterial and the light curing molding ink set of the present inventioncan be suitably used in manufacturing a light cured article by amanufacturing method for light curing molding using an ink-jet scheme.

1. A resin composition for a modeling material, used for shaping amodeling material by a manufacturing method for light curing moldingusing an ink-jet scheme, comprising: (A) an ethylenic unsaturatedmonomer as a photocuring component, (B) a photopolymerization initiator,and (C) a surface adjusting agent, wherein the resin composition for amodeling material has surface tension Mt of 26.0 to 33.0 mN/m, and theresin composition for a modeling material has surface tension Mstrepresented by the following (i) expression of 33.0 mN/m or more.[Mathematic  1]                                     $\begin{matrix}{{Mst} = \frac{\begin{matrix}{\Sigma \mspace{14mu}\left( {{Surface}\mspace{14mu} {tension}\mspace{14mu} {of}\mspace{14mu} {each}\mspace{14mu} {photocuring}\mspace{14mu} {component} \times} \right.} \\\left. {{content}\mspace{14mu} {of}\mspace{14mu} {each}\mspace{14mu} {photocuring}\mspace{14mu} {component}} \right)\end{matrix}}{{Total}\mspace{14mu} {content}\mspace{14mu} {of}\mspace{14mu} {photocuring}\mspace{14mu} {components}}} & (i)\end{matrix}$
 2. The resin composition for a modeling material accordingto claim 1, wherein the (A) component comprises 70 parts by weight orless of a monofunctional ethylenic unsaturated monomer, based on 100parts by weight of the whole resin composition for a modeling material.3. The resin composition for a modeling material according to claim 2,wherein the content of the monofunctional ethylenic unsaturated monomeris 5 to 70 parts by weight, based on 100 parts by weight of the wholeresin composition for a modeling material.
 4. The resin composition fora modeling material according to claim 1, wherein the (A) componentcomprises 70 parts by weight or less of a polyfunctional ethylenicunsaturated monomer, based on 100 parts by weight of the whole resincomposition for a modeling material.
 5. The resin composition for amodeling material according to claim 4, wherein the content of thepolyfunctional ethylenic unsaturated monomer is 20 to 70 parts byweight, based on 100 parts by weight of the whole resin composition fora modeling material.
 6. The resin composition for a modeling materialaccording to claim 1, wherein the content of the (A) component is 80 to99 parts by weight, based on 100 parts by weight of the whole resincomposition for a modeling material.
 7. The resin composition for amodeling material according to claim 1, wherein the resin compositionfor a modeling material further contains an oligomer as (D) aphotocuring component.
 8. The resin composition for a modeling materialaccording to claim 7, wherein the content of the (D) component is 10 to45 parts by weight, based on 100 parts by weight of the whole resincomposition for a modeling material.
 9. The resin composition for amodeling material according to claim 1, wherein the resin compositionfor a modeling material has the surface tension Mst of 33.0 to 40.0mN/m.
 10. A light curing molding ink set used for a manufacturing methodfor light curing molding using an ink-jet scheme, comprising acombination of the resin composition for a modeling material as definedin claim 1, and a resin composition for a supporting material used forshaping the supporting material, wherein the resin composition for asupporting material contains (E) a water-soluble monofunctionalethylenic unsaturated monomer, (F) polyalkylene glycol comprising anoxyethylene group and/or an oxypropylene group, (B) aphotopolymerization initiator, and (C) a surface adjusting agent. 11.The light curing molding ink set according to claim 10, wherein thecontent of the (E) component is 20 to 50 parts by weight, based on 100parts by weight of the whole resin composition for a supportingmaterial.
 12. The light curing molding ink set according to claim 10,wherein the content of the (F) component is 20 to 49 parts by weight,based on 100 parts by weight of the whole resin composition for asupporting material.
 13. The light curing molding ink set according toclaim 10, wherein a number average molecular weight Mn of the (F)component is 100 to 5,000.
 14. The light curing molding ink setaccording claim 10, wherein surface tension St of the resin compositionfor a supporting material is 24.0 to 33.0 mN/m.
 15. A method formanufacturing a light cured article using the light curing molding inkset as defined in claim 10 by a manufacturing method for light curingmolding using an ink-jet scheme, comprising: a step (I) of discharging aresin composition for a modeling material and a resin composition for asupporting material from an ink-jet head, so that a resin compositionlayer in which a layer composed of the resin composition for a modelingmaterial and a layer composed of the resin composition for a supportingmaterial are arranged contiguously, a step (II) of photocuring the resincomposition for a modeling material and the resin composition for asupporting material constituting the resin composition layer,respectively, thereby, obtaining a modeling material and a supportingmaterial, and a step (III) of removing the supporting material, thereby,obtaining a light cured article.